On the Spin Symmetry of Fractional-Occupation Mean-Field Approaches

Abstract

We identify a spin-symmetry dilemma rooted in the representability problem of fractional-occupation densities, which break spin symmetry even for restricted orbital references. We propose a resolution that leverages complex polarization to restore pure-state N-representability and exact spin eigenstates while retaining improvements to the energy and density from occupation smearing. Our results have implications for widely-used smearing methods in solid-state simulation and for their use as a proxy for static correlation in molecules.

arXiv comment9 pages, 4 figures